[go: up one dir, main page]

EP1188717B1 - Méthode de production d'un hydroxyde d'un métal alcalin - Google Patents

Méthode de production d'un hydroxyde d'un métal alcalin Download PDF

Info

Publication number
EP1188717B1
EP1188717B1 EP01121620A EP01121620A EP1188717B1 EP 1188717 B1 EP1188717 B1 EP 1188717B1 EP 01121620 A EP01121620 A EP 01121620A EP 01121620 A EP01121620 A EP 01121620A EP 1188717 B1 EP1188717 B1 EP 1188717B1
Authority
EP
European Patent Office
Prior art keywords
sodium
water
sodium chloride
chloride
solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01121620A
Other languages
German (de)
English (en)
Other versions
EP1188717A1 (fr
Inventor
Fumiaki Nakashima
Shintaro Kikuchi
Hachiro Hirano
Yuriko Takahashi
Shigeru Sakurai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to EP10010209A priority Critical patent/EP2305604A3/fr
Publication of EP1188717A1 publication Critical patent/EP1188717A1/fr
Application granted granted Critical
Publication of EP1188717B1 publication Critical patent/EP1188717B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/18—Preparation by the ammonia-soda process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C01D3/18—Purification with selective solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid

Definitions

  • the present invention relates to a method for producing sodium hydroxide.
  • Sodium chloride is useful as a source material for the production of sodium hydroxide or sodium carbonate or as a snow melting agent or brine.
  • electrolysis employing an ion exchange membrane as a diaphragm hereinafter referred to as ion exchange membrane process (ion exchange membrane process electrolysis)
  • electrolysis employing mercury as an electrode hereinafter referred to as a mercury process (mercury process electrolysis) or electrodialysis
  • an ammonia soda process or an ammonium chloride soda process may, for example, be mentioned.
  • Sodium chloride is required to contain little impurities, when used as a source material for the production of sodium hydroxide or sodium carbonate.
  • sodium chloride of high purity having a small content of calcium, magnesium and SO 4 2- is required in order to improve the quality of the product and to prevent scales which are likely to deposit on the installation in each step.
  • sodium chloride of higher purity is required in order to prevent deterioration of the ion exchange membrane and to maintain the quality of sodium hydroxide as a product.
  • sodium chloride is required to have an extremely small content of calcium, magnesium, strontium, aluminum, iron, lead, mercury, copper, nickel, chromium, cobalt, vanadium, tungsten, manganese, zinc, titanium, molybdenum, tin, tantalum, barium, hafnium, silver, cadmium, gallium, bismuth, cerium, lithium, potassium, silica, SO 4 2- , HSO 3 - , sulfur, ClO 3 - , fluorine, iodine, bromine, boron, phosphorus, selenium, arsenic and organic substances.
  • an acidic gas such as hydrogen chloride or sulfur oxide formed during incineration of municipal waste or industrial waste, used to be removed by using calcium hydroxide as a neutralizing agent in many cases.
  • calcium hydroxide a sodium compound or a potassium compound is used as a neutralizing agent.
  • a sodium compound is inexpensive and made provision easily, and its hydrogen carbonate or carbonate is particularly excellent as a neutralizing agent with relatively low deliquescence.
  • sodium hydroxide, sodium carbonate, sodium sesquicarbonate or sodium hydrogen carbonate may, for example, be mentioned.
  • Such a compound may be a synthetic product or a natural product.
  • sodium chloride will be formed, and such sodium chloride is purified, concentrated and solidified by e.g. a chelating method, a precipitation method wherein it is precipitated as converted to a sulfide or a hydroxide, ultrafiltration, electrodialysis, or an ion exchange membrane method, but it still contains, as impurities, alkali metal sulfates, potassium chloride, iodides, heavy metals, fly ash, activated carbon used for the removal of dioxin, etc. Therefore, the obtained solid salt cannot be recycled and is disposed as landfill, at present. However, the remaining capacities of landfill sites for waste and industrial waste are decreasing, and such waste disposal has become a serious problem in recent years. Accordingly, it is desirable to use such a by-product salt as a source material to produce an alkaline compound again and recycle it.
  • the product can not be used for the production of sodium carbonate by an ammonium chloride soda process, for the production of sodium hydroxide by a mercury process, for the production of sodium hydroxide by ion exchange membrane process, or for the production of sodium hydroxide by electrodialysis, although it may be used for the production of sodium carbonate by an ammonia soda process.
  • product e.g. sodium hydroxide
  • the water which streams into the process with raw material e.g.
  • sodium chloride will be returned to the source material and recycled, and accordingly, if water is introduced separately from outside the system during the production process, the liquid amount in the system increases, and the liquid corresponding to the increased amount is required to be discharged. Accordingly, solid sodium chloride is required.
  • sodium chloride is treated in the form of an aqueous solution and it cannot be used as it is, and it has to be solidified by evaporating water by consumption of a large quantity of energy.
  • the by-product salt may be supplied in a solid, but in the case of the above method, the by-product salt has to be dissolved in water and treated in an aqueous solution, and further, in a case where it is used for a process wherein a solid sodium chloride is used as a source material, it has to be evaporated to crystallization for solidification again after the purification. Further, in an operation to carry out removal of SO 4 2- by means of calcium chloride or barium chloride, there will be also a problem such that a solid waste such as solid calcium sulfate or barium sulfate will be formed anew.
  • DD-A5-288 140 describes a method for the purification of sodium chloride by selectively extracting the impurities.
  • GB-A-220 271 describes a process and apparatus for producing pure table, kitchen and industrial salt from any suitable impure salt, more particularly waste our residual salt and sea salt, or other products containing sodium chloride.
  • the present invention provides a production method for sodium hydroxide, which comprises obtaining a mixture comprising sodium chloride and other water-soluble inorganic salt, which includes sodium iodide by neutralizing a hydrogen chloride containing gas formed during refuse incineration or combustion in a boiler, with sodium hydroxide, sodium carbonate, sodium hydrogencarbonate or sodium sesquicarbonate, adding water or an aqueous solution of said sodium chloride to said mixture in such an amount that is sufficient to dissolve at least sodium iodide substantially in its entire amount and that is not sufficient to dissolve said sodium chloride substantially in its entice amount, thereby to obtain slurry where said sodium iodide is dissolved substantially in its entire amount, subjecting the obtained slurry to solid-liquid separation to recover the solid component (said sodium chloride), and producing sodium hydroxide by electrolysis an aqueous solution of the sodium chloride obtained by means of an ion exchange membrane.
  • the mutual solubility between the sodium chloride to be recovered and other water-soluble inorganic salt is utilized to carry out the operation to form a slurry state such that at least one type of other water-soluble inorganic salt to be removed, is dissolved in the aqueous solution substantially in its entire amount, while the sodium chloride is partially dissolved in the aqueous solution, but the majority of the sodium chloride is present in a solid state without being dissolved.
  • "at least one type of other water-soluble inorganic salt to be removed is dissolved substantially in its entire amount” means that the above water-soluble inorganic salt is dissolved to such an extent that the sodium chloride to be recovered will reach the required intended purity.
  • the slurry is subjected to solid-liquid separation by e.g. filtration and washed preferably with a liquid (such as water) which does not substantially contain said other water-soluble inorganic salt, whereby the solid component will be an sodium chloride which does not substantially contain said other water-soluble inorganic salt.
  • a liquid such as water
  • the sodium chloride to be recovered is a chloride composed of sodium and chlorine and is not a mixture of two or more types of alkali metal chlorides.
  • said other water-soluble inorganic salt to be removed includes also an alkali metal chloride other than the sodium chloride to be purified. Namely, by the method of the present invention, separation of different alkali metal chlorides, which used to be difficult, can readily be carried out to purify sodium chloride.
  • the addition of water or an aqueous solution of the sodium chloride to form a slurry may be carried out in a multiple time dividedly.
  • the purification effects can be improved by carrying out the formation of the slurry and the operation for recovery of the solid component repeatedly. It is effective to carry out the operation repeatedly particularly for removal of a water-soluble inorganic salt which has a low concentration in the mixture and which has an extremely low permissible concentration after the purification.
  • the above solid salt is mixed with water or an aqueous sodium chloride solution (hereinafter referred to generally as water or the like).
  • the aqueous sodium chloride solution may be sea water or dilute brine discharged from the anode side of an electrolyzer in an ion exchange membrane process.
  • an aqueous sodium chloride solution it is preferred that the above impurities are not included in the aqueous solution as far as possible, in order to increase the purification efficiency.
  • the amount of water is not such an amount that is sufficient to dissolve the solid salt in its entirety, but is such an amount that is just sufficient to dissolve sodium sulfate and potassium chloride substantially in their entire amounts or an amount larger by a little than that.
  • the amount of water is not such an amount that is sufficient to dissolve the solid salt in its entirety, but is such an amount that is just sufficient to dissolve sodium sulfate and potassium chloride substantially in their entire amounts or an amount larger by a little than that.
  • centrifugal separation, filtration under reduced pressure, pressure filtration or precipitation separation may, for example, be employed.
  • mother liquor adheres to the solid component obtained by solid-liquid separation, and it is preferred to remove the mother liquor of adhesion by washing with water or the like to obtain solid sodium chloride which does not contain potassium chloride or sodium sulfate.
  • This mother liquor is drained, used as a raw material of a snow melting agent, a raw material of bromine or iodide, etc.
  • the mutual solubility of sodium chloride in the case where other water-soluble inorganic salts are coexistent is usually lower than the solubility of sodium chloride in the case where only sodium chloride and water are present. This serves advantageously for the recovery of sodium chloride in a solid state.
  • the obtained solid component is dissolved in water to carry out solid-liquid separation, whereby an aqueous sodium chloride solution having water-insoluble impurities removed, can be obtained.
  • the obtained aqueous sodium chloride solution can be used as a source material for producing sodium chloride crystals of high purity by evaporating the water or to produce sodium carbonate by an ammonia soda process or an ammonium chloride soda process.
  • the method of the present invention uses ion exchange membrane process which is a major method for producing sodium hydroxide and which is capable of producing a product of high purity.
  • ion exchange membrane process the dilute brine discharged from the anode side after the electrolysis is recycled as a liquid to dissolve solid sodium chloride, and no waste liquid will be effluent. Therefore, if water is additionally introduced into the process system, water in the system will increase unnecessarily, and it will be necessary to discharge the brine out of the system (ion exchange membrane process). Accordingly, as the source material, solid sodium chloride is employed.
  • Sodium chloride obtained in the form of a solid product having other water-soluble inorganic salts removed by the method of the present invention is mixed and dissolved in said dilute brine, followed by solid-liquid separation, and then purified by a conventional method, whereupon it can be used for ion exchange membrane process.
  • the solid salt in the operation of dissolving the solid salt as the source material in water, said dilute brine or the like (hereinafter referred to simply as water or the like), it is preferred to add water or the like so that the concentration of sodium sulfate in the aqueous solution becomes at most 12 mass%, particularly preferably at most 9 mass% reduced to SO 4 concentration based on water whereby substantially the entire amount will be dissolved.
  • water or the like it is preferred to add water or the like so that the potassium chloride concentration in the aqueous solution becomes at most 35 mass%, particularly preferably at most 15 mass%, based on water, whereby it will be dissolved substantially in its entire amount.
  • the solid salt may preliminarily be pulverized and then subjected to the purification treatment.
  • the molar ratio of sodium sulfate to sodium chloride, i.e. sodium sulfate/sodium chloride, in the solid salt is at most 0.15, particularly preferably at most 0.10. If such a molar ratio exceeds 0.15, the amount of sodium chloride tends to be too small to carry out removal of sodium sulfate sufficiently, and the majority of sodium chloride will be dissolved in the solution, whereby the recovery of sodium chloride tends to be low.
  • such a material may be used for Ion exchange membrane process as it is i.e. without removing sodium sulfate, whereby purification by the method of the present invention may not be required.
  • the molar ratio of potassium chloride to sodium chloride, i.e. potassium chloride/sodium chloride, in the solid salt is at most 1.0, particularly preferably at most 0.7. If such a molar ratio exceeds 1.0, the amount of sodium chloride tends to be too small to carry out removal of potassium chloride sufficiently, and the majority of sodium chloride will be dissolved in the solution, whereby the recovery of sodium chloride tends to be low.
  • the concentration of potassium chloride in the solid salt is preferably as low as possible, and it is effective to carry out the purification method of the present invention in a case where potassium chloride is contained in the solid salt even in a small amount (the above molar ratio is more than 0).
  • the preferred range of the molar ratio of other water-soluble inorganic salt to sodium chloride has been described with respect to a two component system wherein water-soluble inorganic salts are sodium chloride and sodium sulfate or a two component system wherein the water-soluble inorganic salts are sodium chloride and potassium chloride.
  • sodium chloride is purified in a three component system comprising, for example, sodium chloride, potassium chloride and sodium sulfate
  • the preferred ranges of the molar ratios of the respective components are decided taking into the mutual solubilities of the three components into consideration.
  • the temperature when the solid salt is dissolved in water or in an aqueous sodium chloride solution is preferably from 0 to 50°C, particularly preferably from 15 to 35°C in a case where sodium sulfate is contained, whereby a residual of dissolution precipitation of sodium sulfate is little, and the recovery of sodium chloride will be high.
  • a temperature range is determined taking into consideration, the temperature dependency of the mutual solubilities of the salt to be purified and impurities, and the optimum temperature range varies depending upon the particular combination of the salt to be purified and impurities.
  • the solubility of sodium sulfate in water is high within the above temperature range.
  • potassium chloride and sodium sulfate are to be removed for purification from a solid salt composed mainly of sodium chloride
  • the amount of water or the like may be adjusted so that potassium chloride can be completely removed by the method of the present invention, while sodium sulfate is not removed in its entire amount and may be removed by means of a conventional desulphurization technique.
  • potassium chloride is removed by the method of the present invention, while sodium sulfate may be reduced to a level of at most 1.0 mass% based on the total mass amount of the solid salt by the method of the present invention, and a conventional technique to remove SO 4 2- may be used in combination.
  • an aqueous solution having the solid salt after removal of potassium chloride, dissolved in water at least one type of substance capable of reacting with a sulfate to form a compound having a low solubility in water, such as calcium hydroxide, barium chloride, calcium chloride, a heavy metal, calcium or magnesium, is added, followed by solid-liquid separation, whereby SO 4 2- will be removed, and an aqueous sodium chloride solution having a high purity can be obtained.
  • aqueous sodium chloride solution to be treated by contacting the aqueous sodium chloride solution to be treated, with a chelate resin, it is possible to reduce calcium, magnesium, strontium, barium, mercury, etc., whereby an aqueous sodium chloride solution of higher purity can be obtained.
  • the method of removing sodium sulfate and potassium chloride from sodium chloride has been described in detail.
  • the method of the present invention is not limited thereto, and by the method of the present invention, various water-soluble inorganic components included in small amounts respectively, can be removed simultaneously. Namely, it is possible to remove water-soluble inorganic components, such as heavy metal chloride compounds, a bromine compound such as sodium bromide, an iodine compound, a fluorine compound, and a sodium compound such as sodium chlorate, which used to be difficult to remove by a conventional calcium chloride-addition method or an ion exchange resin method.
  • the allowable concentration of iodine in sodium chloride is very low. Accordingly, the method of the present invention is used, whereby water-soluble sodium iodide can be removed to a very low concentration from high iodide content of a solid sodium chloride (e.g. a by-product salt).
  • a solid sodium chloride e.g. a by-product salt
  • sodium iodide in the case of removing sodium iodide from a solid salt composed mainly of sodium chloride, in the operation wherein the solid salt is mixed with water or the like to partially dissolve sodium chloride and to dissolve other water-soluble inorganic salts substantially in their entire amounts, it is preferred to add water or the like so that sodium iodide becomes to be at most 5 mass%, particularly preferably at most 2 mass%, reduced to iodine concentration, based on water or the like. By adjusting the amount of water or the like to such a level, sodium iodide will be dissolved substantially in its entire amount.
  • the molar ratio of sodium iodide to sodium chloride, i.e. sodium iodide/sodium chloride, in the solid salt is preferably at most 0.01, particularly preferably at most 0.005.
  • sodium chloride is used as a source material in ion exchange membrane process
  • iodine is usually required to be at most 1 mass ppm. Accordingly, in a case where the content of iodine in the solid salt is large as a source material, it is required to repeat the method of the present invention in a plurality of times. Specifically, in a case where the above molar ratio exceeds 0.01, it will be required to repeat the method at least 5 times, and thus, it is lingered over the operation.
  • the water-soluble sodium iodide may be partially removed by this method, and a conventional technique for removal of iodine, such as removal by means of a chelate resin or the like, may be used in combination.
  • concentration of sodium iodide in the solid salt is preferably as low as possible, it is effective to carry out the purification of the present invention in a case where sodium iodide is contained in the solid salt even in a small amount (the above molar ratio is more than 0).
  • the solid sodium chloride obtained by the above treatment may be dissolved in water or the like and subjected to solid-liquid separation again, whereby it is possible to obtain an aqueous sodium chloride solution having water-insoluble impurities removed.
  • a by-product salt formed by the treatment of an exhaust gas from a waste incineration plant with a sodium compound usually contains an oxide of heavy metal, activated carbon, silica, aluminosilicate, etc., as components of fly ash leaked from an electric dust collector.
  • such water-insoluble components can be removed by solid-liquid separation.
  • metals such as calcium, magnesium, strontium, aluminum, iron, lead, mercury, copper, nickel, chromium, cobalt, vanadium, tungsten, manganese, zinc, titanium, molybdenum, tin, tantalum, barium, hafnium, silver, cadmium, gallium, bismuth, cerium, lithium and potassium, silica, SO 4 2- , HSO 3 - , ClO 3 - , fluorine, iodine, bromine, boron, phosphorus, selenium, arsenic, organic substances, etc.
  • Solid sodium chloride obtained in the present invention is used for the production of sodium hydroxide by electrolysis by means of ion exchange membrane process. Further, even in a case where it is used for the production of an aqueous sodium hydroxide solution by ion exchange membrane process where the iodine concentration is limited, an installation employing e.g. an ion exchange resin for removal of iodine will not be required, or the scale of such an installation can be made small. Namely, as compared with a conventional method, the installation cost or the running cost can be made small.
  • the salt to be purified in the present invention is a by-product salt obtained by neutralization of an acidic gas containing hydrogen chloride in a combustion gas from a municipal waste incineration plant or an industrial waste incineration plant, with a sodium compound.
  • the sodium compound is sodium hydroxide, sodium carbonate, sodium sesquicarbonate or sodium hydrogen carbonate, and such a compound may be a synthetic product or a natural product.
  • Such a sodium compound is reacted with an acidic gas in the gas by a wet process or dry process gas treating installation to form a by-product salt wherein sodium chloride, sodium sulfate, etc. are mixed.
  • potassium chloride or a metal iodide is usually contained as an impurity.
  • the production process of such a by-product salt may vary, but the by-product salt (in a case where the by-product salt is obtainable as dissolved in an aqueous solution, the component dissolved in the aqueous solution) will basically have the same composition although the residual amount of alkali not-reacted with the acidic gas may vary, and the method of the present invention may be applied to such a by-product salt.
  • a sodium chloride-containing solid salt which does not contain sodium sulfate, potassium chloride or iodine, and which used to be technically difficult to recover by conventional treatment of hydrogen chloride formed from e.g. a waste incineration plant.
  • FIG. 1 is a chart illustrating a conventional wet process neutralization treatment process of an exhaust gas, wherein e.g. an exhaust gas formed at a municipal waste incineration plant is treated for neutralization in a wet process to obtain a by-product salt.
  • An exhaust gas G1 containing hydrogen chloride and sulfur oxide formed in a stoker fired furnace type waste incinerator 11 is passed through a waste heat boiler 12 and an economizer 13 for heat recovery and then introduced into an electrostatic precipitator 14, wherein fly ash S1 is removed.
  • the exhaust gas G1 is sent to an exhaust gas cleaning tower (scrubber) 17 via a gas air heat exchanger 15 and an induced draftfan 16, and reacted with an aqueous sodium hydroxide solution, whereby acidic gas components such as hydrogen chloride, sulfur oxide, etc. in the exhaust gas G1 will be neutralized and removed.
  • the exhaust gas G2 treated for neutralization is then discharged from a stack 20 via a steam type gas heater 18 and a silencer 19.
  • the reaction product (liquid) of the exhaust gas G1 with the aqueous sodium hydroxide solution in the exhaust gas cleaning tower 17, is sent to a flocculation setting facility 21 as waste water of scrubber L1.
  • the waste water of scrubber L1 contains sodium chloride, sodium sulfate, sodium iodide, etc.
  • a chelate agent and a flocculant are added, followed by solid-liquid separation, whereby the precipitate formed by the reaction is disposed via a sludge treatment facility not shown.
  • the chelate agent EPOFLOCK L-1 (trade name) manufactured by Miyoshi Oil & Fat Co., Ltd.
  • ACLEAN M (trade name) manufactured by Asahi Glass Engineering Co., Ltd. is, for example, used, and as the flocculant, a polymer flocculant such as AQUALIC FHG (trade name), KURIFLOCK (trade name) or KURIFIX CP-933 (trade name), manufactured by Kurita Water Industries Ltd., or AQLEAN F (trade name) manufactured by Asahi Glass Engineering Co., is used.
  • AQUALIC FHG trade name
  • KURIFLOCK trade name
  • KURIFIX CP-933 trade name
  • Clarified liquid L2 obtained by the treatment in the flocculation setting facility 21 is then passed through a sand filter 22 and purified by a neutralization tank 23, a chelate resin tower 25 and an activated carbon tower 25, and then, the water is removed by a dryer 26 for solidification to obtain a solid by-product salt S2.
  • This by-product salt S2 is substantially free from heavy metals or insoluble components, but still contains sodium sulfate, potassium chloride, an iodine compound, etc. in addition to sodium chloride. Accordingly, it can not be used for e.g. ion exchange membrane process simply by removing calcium or magnesium.
  • FIG. 2 is a chart illustrating a conventional dry neutralization treatment process of an exhaust gas, wherein e.g. an exhaust gas formed at a municipal waste incineration plant is treated for neutralization in a dry process to obtain a by-product salt.
  • an exhaust gas G1 formed by a stoker fired furnace type waste incinerator 11 is passed through a waste heat boiler 12 and an economizer 13 for heat recovery and then sent to an exhaust gas cooling tower 31.
  • the exhaust gas G1 is cooled to a temperature lower than the temperature for synthesis of dioxins, and then reacted with activated carbon and powdery neutralizing agent blown thereto.
  • dioxins are removed from the exhaust gas by the activated carbon.
  • the powdery neutralizing agent sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate may, for example, be used, and hydrogen chloride, sulfur oxide, etc. in the exhaust gas G1 will be reacted with the powdery neutralizing agent to form a by-product salt.
  • the powdery neutralizing agent calcium hydroxide or the like, may be combined.
  • calcium hydroxide has a problem such that it is required in a large excess relative to hydrogen chloride content in the exhaust gas, and it forms a solid waste even if it is dissolved in water.
  • the by-product salt S2' containing fly ash, formed by the reaction with the powdery neutralizing agent, is removed by a bag filter 32, and the exhaust gas G2 treated for neutralization is discharged from a chimney via an induction ventilator 33.
  • the by-product salt S2' collected by the bag filter 32 has a purity further lower than the by-product salt S2 obtained in the process of FIG. 1 , as it contains insoluble components such as heavy metals, fly ash and activated carbon, and it can not be used as it is for e.g. ion exchange process.
  • FIG. 3 is a chart illustrating a purification process of a by-product salt as an embodiment of the present invention, which shows a process for purifying the by-product salt S2 (S2') formed by the treatment by the process of FIG. 1 or 2 to such an extent that it can be used for a process for producing an aqueous sodium hydroxide solution by ion exchange process.
  • the by-product salt S2 (S2') is sent to a mixing tank 41, where water or an aqueous solution containing sodium chloride such as dilute brine, is introduced to obtain a slurry SL1 wherein the by-product salt S2 (S2') is partially dissolved.
  • the slurry SL1 among water-soluble inorganic salts, only sodium chloride is present substantially as a solid component, and other water soluble inorganic salts are substantially dissolved in the liquid.
  • the slurry SL1 is subjected to solid-liquid separation by a filter 42 and further washed (rinsed mother liquor out of the filter cake), as the case requires.
  • a separation apparatus having a washing function such as a horizontal belt filter (a vacuum filter), a cylindrical vacuum filter (an oliver filter), a filter press or a basket type centrifugal separator, is preferred.
  • SO 4 2- , potassium, iodine, etc. are removed as contained in the liquid L3 (mother liquor).
  • the slurring and solid-liquid separation process up to here, may be repeated, as shown by a broken line in FIG. 3 .
  • a crude purified salt S3 separated as solid is sent to a dissolution tank 43 and dissolved in water or in an aqueous solution containing sodium chloride such as dilute brine, which is supplied to the dissolution tank 43, and then a solid S4 insoluble in water is separated and removed by a filter 44.
  • the filtrate from the filter 44 is further mixed with sodium hydroxide, sodium carbonate, a chelate agent and a polymer flocculant in a reaction tank 45 to form a precipitate S5 such as hydroxides of calcium, magnesium, heavy metals, etc.
  • the mixture is sent to a clarifying tank 46 (clarifier), wherein the precipitate S5 is removed.
  • a filter such as a filter press or a vacuum filter
  • the clarified liquid L4 from the clarifier tank 46 is sent to a filter 47, and a solid contained in a very small amount, will be removed.
  • a chelate resin tower 48 calcium, magnesium, strontium, etc., are removed to a higher degree, to obtain a highly purified brine L5.
  • filters 44 and 47 sand filters, precoat filters, cartridge filters or filter press, may, for example, be used.
  • This highly purified brine L5 has such a purity that is applicable to ion exchange membrane process, and can be supplied to an ion exchange membrane type electrolyzer, whereby an aqueous sodium hydroxide solution of high purity can be obtained by ion exchange membrane process.
  • the solution thereby filtered will be referred to as a primary purified brine.
  • 52 kg of this primary purified brine was taken and passed through a first small size column packed with 140 g of an amino phosphate type ion exchange resin (DUOLITE C467, trade name, manufactured by Sumitomo Chemical Co., Ltd.) at a liquid superficial velocity of 20 m/hr.
  • the liquid superficial velocity is a value obtained by dividing the liquid flow rate (m 3 /hr) by the cross-sectional area (m 2 ) of the column.
  • the liquid passed through the first small size column was then passed through a second small size column packed with 140 g of a styrene type micro porous ion exchange resin (DUOLITE A161TRSO4, trade name, manufactured by Sumitomo Chemical Co., Ltd.) to remove iodine, whereby a purified brine (hereinafter referred to as a secondary purified brine) was obtained.
  • a purified brine hereinafter referred to as a secondary purified brine
  • Table 1 The analytical values of the by-product salt, the crude purified salt, the primary purified brine and the secondary purified brine, respectively, are shown in Table 1. Further, in this example, the desired value for the purity of the aqueous sodium chloride solution for the application to ion exchange membrane process was as shown in Table 1.
  • an ion exchange membrane (FLEMION F-795, trade name, manufactured by Asahi Glass Co., Ltd.) was set in a monopolar electrolyzer having an electrolytic area of 5 cm x 5 cm, and a continuous operation was carried out for 90 days at a current density of 3 kA/m 2 at a temperature of 85°C at a sodium hydroxide concentration in a cathode compartment of 32 mass%, using the above-mentioned secondary purified brine as sodium chloride in an anode compartment at a sodium chloride concentration of 210 g/l.
  • the relation between the number of days and the current efficiency is shown in Table 2. The current efficiency did not decrease even upon expiration of 90 days. Table 2 Number of days (days) 2 30 60 90 Current efficiency (%) 95.8 95.8 95.8 95.8
  • This slurry was subjected to filtration by a Nutsche filter using a filter paper of 5A, and 6 kg of a saturated aqueous solution having 25 mass% of sodium chloride of guaranteed reagent dissolved in water, was sprayed to the filter cake to wash off the mother liquor of adhesion.
  • the solid was recovered from the filter paper, whereby 16 kg of a salt (hereinafter referred to as a crude purified salt) was recovered. 16 kg of this crude purified salt was dissolved in 26 kg of pure water, and solid sodium sulfate was added so that the concentration of SO 4 2- in the liquid would be about 0.2 mass% (hereinafter referred to as a crude purified brine).
  • a primary purified brine 43 kg of the crude purified brine was subjected to filtration by a Nutsche filter using a filter paper of 5A to separate the solid, and then to the filtrate, 4.3 g of a chelate agent (EPOFLOCK, trade name, manufactured by Miyoshi Oil & Fat Co., Ltd.) and 15 g of iron chloride were added, followed by stirring for 30 minutes.
  • a cationic polymer flocculant (KURIFIX CP-933, trade name, manufactured by Kurita Water Industries Ltd.) was added for clarification and separation, followed by filtration by a Nutsche filter using a filter paper of 5A to obtain a purified brine (hereinafter referred to as a primary purified brine).
  • Example 4 In the same manner as in Example 1 except that the above tertiary purified brine was used as sodium chloride in the anode cell, ion exchange membrane process was carried out under the same conditions as in Example 1. The relation between the number of days and the current efficiency is shown in Table 4. The current efficiency did not decrease even after expiration of 90 days. Table 4 Number of days (days) 2 30 60 90 Current efficiency (%) 95.8 95.8 95.8 95.7
  • alkali metal chlorides such as a combination of sodium chloride and potassium chloride
  • potassium chloride can be removed to recover sodium chloride.
  • sodium chloride can be purified by removing such a water-soluble metal sulfate without forming a new solid waste.
  • iodine can be removed to an extremely low concentration by the method of the present invention.
  • the sodium chloride can be purified to such a high purity that it is industrially useful as a source material for ion exchange membrane process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Treating Waste Gases (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Claims (8)

  1. Une méthode de production d'un hydroxyde de sodium, qui comprend :
    (a) l'obtention d'un mélange comprenant du chlorure de sodium et un autre sel inorganique hydrosoluble, qui comprend de l'iodure de sodium, en neutralisant un gaz contenant du chlorure d'hydrogène formé durant l'incinération ou la combustion de déchets dans une chaudière, avec de l'hydroxyde de sodium, du carbonate de sodium, de l'hydrogénocarbonate de sodium ou du sesquicarbonate de sodium,
    (b) l'ajout d'eau ou d'une solution aqueuse dudit chlorure de sodium au mélange obtenu à l'étape (a) dans une quantité telle qu'elle soit suffisante pour dissoudre au moins substantiellement l'iodure de sodium dans sa quantité totale et qui ne soit pas suffisante pour dissoudre substantiellement ledit chlorure de sodium dans sa quantité totale, pour obtenir ainsi une bouillie où ledit iodure de sodium est dissout substantiellement dans sa quantité totale,
    (c) la soumission de la bouillie obtenue dans l'étape (b) à une séparation solide-liquide afin de récupérer le chlorure de sodium en tant que composant solide, et
    (d) la production d'hydroxyde de sodium par électrolyse d'une solution aqueuse du chlorure de sodium obtenu à l'étape (c) au moyen d'une membrane échangeuse d'ions.
  2. La méthode selon la revendication 1, dans laquelle de l'eau ou une solution aqueuse dudit chlorure de sodium dans l'étape (d) est une saumure diluée déchargée depuis le côté anode d'un appareil d'électrolyse dans un procédé de membrane échangeuse d'ions.
  3. La méthode selon l'une quelconque des revendications 1 ou 2, dans laquelle le composant solide obtenu par séparation solide-liquide de la bouillie dans l'étape (c), est dissoute à nouveau dans de l'eau et ensuite à nouveau soumise à une séparation solide-liquide afin d'éliminer les impuretés non hydrosolubles et ainsi récupérer ledit chlorure de sodium sous la forme d'une solution aqueuse.
  4. La méthode selon la revendication 3, dans laquelle les impuretés non hydrosolubles contiennent un oxyde de métal lourd, du charbon actif, de la silice, des aluminosilicates en tant que composants de cendres volantes.
  5. La méthode selon l'une quelconque des revendications 1 à 4, dans laquelle au moins un type dudit autre sel inorganique hydrosoluble est un iodure de métal hydrosoluble.
  6. La méthode selon la revendication 1, comprenant en outre la purification de la solution aqueuse contenant le chlorure de sodium récupéré par élimination des composés de chlorure de métal lourd.
  7. La méthode selon l'une quelconque des revendications 1 à 6, dans laquelle, dans l'étape (b), ledit mélange contient de l'iodure de sodium en tant qu'autre sel hydrosoluble dans une quantité d'au plus 0,01 fois par mol par rapport au chlorure de sodium.
  8. La méthode selon la revendication 7, dans laquelle, dans la bouillie obtenue dans l'étape (b), sur la base de l'eau, la concentration d'iodure de sodium réduite en concentration d'iode devient au plus 5% en masse.
EP01121620A 2000-09-13 2001-09-11 Méthode de production d'un hydroxyde d'un métal alcalin Expired - Lifetime EP1188717B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10010209A EP2305604A3 (fr) 2000-09-13 2001-09-11 Procédé de purification d'un chlorure d'un métal alcalin et méthode de production d'un hydroxyde d'un métal alcalin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000278616 2000-09-13
JP2000278616 2000-09-13

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP10010209.4 Division-Into 2010-09-22

Publications (2)

Publication Number Publication Date
EP1188717A1 EP1188717A1 (fr) 2002-03-20
EP1188717B1 true EP1188717B1 (fr) 2011-06-15

Family

ID=18763751

Family Applications (2)

Application Number Title Priority Date Filing Date
EP01121620A Expired - Lifetime EP1188717B1 (fr) 2000-09-13 2001-09-11 Méthode de production d'un hydroxyde d'un métal alcalin
EP10010209A Withdrawn EP2305604A3 (fr) 2000-09-13 2001-09-11 Procédé de purification d'un chlorure d'un métal alcalin et méthode de production d'un hydroxyde d'un métal alcalin

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP10010209A Withdrawn EP2305604A3 (fr) 2000-09-13 2001-09-11 Procédé de purification d'un chlorure d'un métal alcalin et méthode de production d'un hydroxyde d'un métal alcalin

Country Status (3)

Country Link
US (1) US20020054841A1 (fr)
EP (2) EP1188717B1 (fr)
ES (1) ES2367627T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104192868A (zh) * 2014-08-25 2014-12-10 连云港树人科创食品添加剂有限公司 一种除去氯化钾中抗结剂的方法

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2285153T3 (es) * 2002-03-08 2007-11-16 Drm, Dr. Muller Ag Metodo para la filtracion continua de una salmuera bruta que se utiliza en la electrolisis del cloro alcali.
WO2006111164A1 (fr) * 2005-04-18 2006-10-26 Jan Procida Méthode de production sous une forme pure de sels halogénés de métaux alcalins et/ou alcalino-terreux obtenus par traitement hydrolytique de déchets organiques halogénés
DE102007027705A1 (de) * 2007-06-15 2008-12-18 Ziemann Ludwigsburg Gmbh Verfahren zum Behandeln von Flüssigkeiten führenden Anlagen, insbesondere von Brauerei- und Getränkeanlagen, und deren Teile, und Vorrichtung zum Durchführen des Verfahrens
US9527003B2 (en) * 2009-06-02 2016-12-27 Hudgens Holdings, Llc Subterranean well production saltwater evaporation station with iodine separator
US10184077B2 (en) 2009-06-02 2019-01-22 Hudgens Holdings, Llc Subterranean well production saltwater evaporation station with saltwater recycle
FR2951383B1 (fr) 2009-10-20 2012-09-21 Solvay Procede pour la valorisation conjointe de sels solubles contenus dans un residu d'un procede industriel
US20150352498A1 (en) * 2011-08-17 2015-12-10 Ahilan RAMAN Process and system for producing sodium chloride brine
KR101464673B1 (ko) 2012-05-07 2014-11-28 한화케미칼 주식회사 에틸렌아민류 제조시 생성되는 염화나트륨의 정제 방법
WO2013168972A1 (fr) * 2012-05-07 2013-11-14 Hanwha Chemical Corporation Procédé de purification du chlorure de sodium dans le procédé de production d'éthylène amines
CN111592024B (zh) * 2020-04-24 2022-09-06 广西科学院 一种氯化钙制备亚微细实心球形碳酸钙的方法
CN113355517B (zh) * 2021-05-31 2022-07-26 云南罗平锌电股份有限公司 一种在锌冶炼过程中无害化处理回收镁氟污酸的方法
CN114890439A (zh) * 2022-05-17 2022-08-12 上海大学 一种工业废盐分离纯化的装置
CN115970482A (zh) * 2022-12-23 2023-04-18 中盐金坛盐化有限责任公司 一种烟道气净化及卤水净化精制消毒盐的方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE282952C (fr) *
GB220271A (en) * 1923-08-06 1925-03-18 Max Kruger Process and apparatus for producing pure table, kitchen and industrial salt from anysuitable impure salt, more particularly residual or pickling salt and sea salt
FR795557A (fr) * 1934-12-22 1936-03-17 Verwertung Chemisch Tech Verfa Procédé pour la purification physique du chlorure de sodium
ES350275A1 (es) * 1967-02-01 1969-05-01 Sincat Spa Procedimiento para la purificacion de cloruro sodico.
AU2603588A (en) * 1987-10-07 1989-05-02 Gerald J. Grott Method of reforming soluble salts to effect purification and increase crystal size thereof
DD288140A5 (de) * 1989-09-29 1991-03-21 Veb Kalibatrieb Suedharz,De Verfahren zum reinigen von natriumchlorid
IT1248564B (it) * 1991-06-27 1995-01-19 Permelec Spa Nora Processo di decomposizione elettrochimica di sali neutri senza co-produzione di alogeni o di acido e cella di elettrolisi adatta per la sua realizzazione.
FR2679221B1 (fr) * 1991-07-19 1994-07-01 Solvay Procede de fabrication d'une solution aqueuse de chlorure de sodium et son utilisation.
BE1005291A3 (fr) * 1991-09-10 1993-06-22 Solvay Procede de fabrication d'une solution aqueuse industrielle de chlorure de sodium et utilisation de la solution aqueuse de chlorure de sodium ainsi obtenue pour la fabrication electrolytique d'une solution aqueuse d'hydroxyde de sodium, pour la fabrication de carbonate de sodium et pour la fabrication de cristaux de chlorure de sodium.
IT1291996B1 (it) * 1997-05-26 1999-01-25 Consorzio Obbligatorio Naziona Composto reattivo per la rimozione di composti acidi da fumi o gas ad alta temperatura e procedimento per la sua preparazione

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104192868A (zh) * 2014-08-25 2014-12-10 连云港树人科创食品添加剂有限公司 一种除去氯化钾中抗结剂的方法

Also Published As

Publication number Publication date
EP2305604A3 (fr) 2011-06-29
EP2305604A2 (fr) 2011-04-06
ES2367627T3 (es) 2011-11-07
US20020054841A1 (en) 2002-05-09
EP1188717A1 (fr) 2002-03-20

Similar Documents

Publication Publication Date Title
RU2713360C2 (ru) Способ получения моногидрата гидроксида лития из рассолов
EP1188717B1 (fr) Méthode de production d'un hydroxyde d'un métal alcalin
US8603344B2 (en) Method and apparatus for removing metal from waste water
CN108698827B (zh) 用于从废水中生产磷产品的方法
RU2732034C2 (ru) Способ и устройство для извлечения соли
AU666328B2 (en) Producing aqueous industrial sodium hydroxide solution
JP5290918B2 (ja) アルカリ金属塩化物、アルカリ金属水酸化物の製造方法
CN102574024B (zh) 用于对包含在工业过程的残留物中的可溶盐类进行联合再生的方法
JP2001026418A (ja) 工業的に有用な無機材料の回収方法及び該回収方法によって回収した工業的に有用な無機材料
US4087359A (en) Process for removing mercury and mercury salts from liquid effluents
CN112794534A (zh) 飞灰资源化利用处理系统及方法
US6692720B1 (en) Method for producing sodium chloride crystals
CN112225242A (zh) 一种垃圾焚烧飞灰与盐酸反应的母液的资源化处理装置及工艺
US5474581A (en) Method for producing an aqueous sodium chloride solution and use thereof
JP5114820B2 (ja) 塩化ナトリウムの精製方法及び水酸化ナトリウムの製造方法
US20180050919A1 (en) Process for manufacturing an aqueous sodium chloride solution
JP2004359516A (ja) アルカリ金属塩化物、アルカリ金属水酸化物の製造方法
US4012297A (en) Mercury recovery and recycle process
JP5032784B2 (ja) 塩化ナトリウムの製造システム
CN113636634A (zh) 一种从含氯工业废水中分离回收氯的方法
KR100695193B1 (ko) 2,4,6-트리머캅토-ｓ-트리아진 알칼리금속염의 제조 방법
JP2960876B2 (ja) 銅電解液の浄液方法
CN117383721A (zh) 一种回收高纯度氢氧化镁的脱硫废水处理方法及系统
CN116903019A (zh) 一种高含氟含氯危废焚烧飞灰处理方法
WO2023038541A1 (fr) Procédé de production de sels de bromure

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20020411

AKX Designation fees paid

Free format text: BE DE ES FR GB IT

17Q First examination report despatched

Effective date: 20040109

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: METHOD FOR PRODUCING AN ALKALI METAL HYDROXIDE

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60144782

Country of ref document: DE

Effective date: 20110721

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: ASAHI GLASS COMPANY, LIMITED

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2367627

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20111107

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20120316

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60144782

Country of ref document: DE

Effective date: 20120316

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20120905

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20120912

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20121004

Year of fee payment: 12

BERE Be: lapsed

Owner name: ASAHI GLASS CO., LTD.

Effective date: 20130930

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130911

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130911

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130930

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20141007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130912

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20150922

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20150922

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20150924

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60144782

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170401

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160911